Unravelling the Enigma of Nonoxidative Conversion of Methane on Iron Single-Atom Catalysts

The direct, nonoxidative conversion of methane on a silica-confined single-atom iron catalyst is a landmark discovery in catalysis, but the proposed gas-phase reaction mechanism is still open to discussion. Here, we report a surface reaction mechanism by computational modeling and simulations. The activation of methane occurs at the single iron site, whereas the dissociated methyl disfavors desorption into gas phase under the reactive conditions. In contrast, the dissociated methyl prefers transferring to adjacent carbon sites of the active center (Fe₁©SiC₂), followed by C−C coupling and hydrogen transfer to produce the main product (ethylene) via a key −CH−CH₂ intermediate. We find a quasi Mars–van Krevelen (quasi-MvK) surface reaction mechanism involving extracting and refilling the surface carbon atoms for the nonoxidative conversion of methane on Fe₁©SiO₂ and this surface process is identified to be more plausible than the alternative gas-phase reaction mechanism.     

General Formation of Macro-/Mesoporous Nanoshells from Interfacial Assembly of Irregular Mesostructured Nanounits

Mesoporous core–shell nanostructures with controllable ultra-large open channels in their nanoshells are of great interest. However, soft template-directed cooperative assembly to mesoporous nanoshells with highly accessible pores larger than 30 nm, or even above 50 nm into macroporous range, remains a significant challenge. Herein we report a general approach for precisely tailored coating of hierarchically macro-/mesoporous polymer and carbon shells, possessing highly accessible radial channels with extremely wide pore size distribution from ca. 10 nm to ca. 200 nm, on diverse functional materials. This strategy creates opportunities to tailor the interfacial assembly of irregular mesostructured nanounits on core materials and generate various core–shell nanomaterials with controllable pore architectures. The obtained Fe,N-doped macro-/mesoporous carbon nanoshells show enhanced electrochemical performance for the oxygen reduction reaction in alkaline condition.     

Micron-Sized Zeolite Beta Single Crystals Featuring Intracrystal Interconnected Ordered Macro-Meso-Microporosity Displaying Superior Catalytic Performance

Zeolite Beta single crystals with intracrystalline hierarchical porosity at macro-, meso-, and micro-length scales can effectively overcome the diffusion limitations in the conversion of bulky molecules. However, the construction of large zeolite Beta single crystals with such porosity is a challenge. We report herein the synthesis of hierarchically ordered macro-mesoporous single-crystalline zeolite Beta (OMMS-Beta) with a rare micron-scale crystal size by an in situ bottom-up confined zeolite crystallization strategy. The fully interconnected intracrystalline macro-meso-microporous hierarchy and the micron-sized single-crystalline nature of OMMS-Beta lead to improved accessibility to active sites and outstanding (hydro)thermal stability. Higher catalytic performances in gas-phase and liquid-phase acid-catalyzed reactions involving bulky molecules are obtained compared to commercial Beta and nanosized Beta zeolites. The strategy has been extended to the synthesis of other zeolitic materials, including ZSM-5, TS-1, and SAPO-34.     

Fabricating Dual-Atom Iron Catalysts for Efficient Oxygen Evolution Reaction: A Heteroatom Modulator Approach

Understanding the thermal aggregation behavior of metal atoms is important for the synthesis of supported metal clusters. Here, derived from a metal–organic framework encapsulating a trinuclear Fe^III₂Fe^II complex (denoted as Fe₃) within the channels, a well-defined nitrogen-doped carbon layer is fabricated as an ideal support for stabilizing the generated iron nanoclusters. Atomic replacement of Fe^II by other metal(II) ions (e.g., Zn^II/Co^II) via synthesizing isostructural trinuclear-complex precursors (Fe₂Zn/Fe₂Co), namely the “heteroatom modulator approach”, is inhibiting the aggregation of Fe atoms toward nanoclusters with formation of a stable iron dimer in an optimal metal–nitrogen moiety, clearly identified by direct transmission electron microscopy and X-ray absorption fine structure analysis. The supported iron dimer, serving as cooperative metal–metal site, acts as efficient oxygen evolution catalyst. Our findings offer an atomic insight to guide the future design of ultrasmall metal clusters bearing outstanding catalytic capabilities.     

Measurement of Residual Dipolar Couplings of Organic Molecules in Multiple Solvent Systems Using a Liquid-Crystalline-Based Medium

Residual dipolar coupling (RDC), a robust anisotropic NMR parameter for structural elucidation of organic molecules, is only accessible in an anisotropic environment. Herein, we introduce a novel alignment medium based on the molecular self-assembly of oligopeptide amphiphile (OPA). This medium is compatible with different intermediate and polar solvent systems, such as CD₃OD, [D₆]DMSO, and D₂O. The preparation of the OPA-based medium is simple and rapid, while only very weak background signals were observed from OPAs. Furthermore, we show that the purity of OPA has only a minor influence on the quality of the RDC data. These advantages allow RDC measurements of organic molecules with different polarities and solubilities with high efficiency and accuracy.     

Manipulating Light-Induced Dynamic Macro-Movement and Static Photonic Properties within 1D Isostructural Hydrogen-Bonded Molecular Cocrystals

Smart molecular crystals with light-driven mechanical responses have received interest owing to their potential uses in molecular machines, artificial muscles, and biomimetics. However, challenges remain in control over both the dynamic photo-mechanical behaviors and static photonic properties of molecular crystals based on the same molecule. Herein, we show the construction of isostructural co-crystals allows their light-induced cracking and jumping behaviors (photosalient effect) to be controlled. Hydrogen-bonded co-crystals from 4-(1-naphthylvinyl)pyridine ( NVP ) with co-formers (tetrafluoro-4-hydroxybenzoic acid ( THA ) and tetrafluorobenzoic acid ( TA )) crystallize as isostructural crystals, but have different static and dynamic photo-mechanical behaviors. These differences are due to alternations in the orientation of NVP and hydrogen-bonding modes of the co-formers. After light activation, the 1D NVP-TA crystal splits and shears off within 1 s. For NVP-THA , its photostability and high quantum yield give novel photonic properties, including low optical waveguide loss, highly polarized anisotropy, and efficient up-conversion fluorescence.     

Sensitive and selective determination of 4-nitrophenol in water and food using modified polyethyleneimine-capped carbon dots

Hazardous 4-nitrophenol (4-NP) has created serious threats to humans and the environment; therefore, it is highly desirable to develop a facile and practical method for the monitoring of 4-NP in environment and food. Here, a fluorescence method based on modified polyethyleneimine-capped carbon dots (mPEI-CDs) was developed for sensitive and selective determination of 4-NP in water, fruit, and vegetable samples. First, highly fluorescent mPEI-CDs (quantum yield about 40.3%) were easily synthesized via a one-step hydrothermal method by using novel acetic anhydride modified polyethyleneimine (mPEI) and citric acid as precursors. Compared to the unmodified PEI-CDs, the acetic anhydride mPEI-CDs exhibited excellent fluorescent stability in a wider pH range of 4.0–9.0. Under pH 8.0, a selective determination of 4-NP was achieved based on the inner filter effect (IFE) mechanism. After optimization, good linear relationships between fluorescence intensity function (F₀-F)/F₀ and the concentration of 4-NP were obtained in ranges of 0.5–10 and 10–100 μM, respectively, while efficiently avoiding the interferences from two other nitrophenol isomers, possible coexisting metal cations and anions in samples. Finally, the proposed approach was successfully applied for the determination of 4-NP in water, honey, strawberry, and tomato samples.     

Free control of far-field scattering angle of transmission terahertz wave using multilayer split-ring resonators’ metasurfaces

To enhance transmission efficiency of Pancharatnam–Berry (PB) phase metasurfaces, multilayer splitring resonators were proposed to develop encoding sequences. As per the generalized Snell’s law, the deflection angle of the PB phase encoding metasurfaces depends on the metasurface period’s size. Therefore, it is impossible to design an infinitesimal metasurface unit; consequently, the continuous transmission scattering angle cannot be obtained. In digital signal processing, this study introduces the Fourier convolution principle on encoding metasurface sequences to freely control the transmitted scattering angles. Both addition and subtraction operations between two different encoding sequences were then performed to achieve the continuous variation of the scattering angle. Furthermore, we established that the Fourier convolution principle can be applied to the checkerboard coded metasurfaces.     

Synthesis of Caffeic Acid Sulphonamide Derivatives and Preliminary Exploration of Their Biological Applications

Structural modification of native compounds is an effective way to develop new drugs with increased pharmacological activities and improved material characteristics. In this study, caffeic acid sulphonamide derivatives(CSs) were synthesised by conjugating sulphonamides to the backbone of caffeic acid. The structures of these derivatives were elucidated by means of Fourier transform infrared spectroscopy(FTIR), ¹H NMR, ¹³C NMR, and electrospray ionization mass spectroscopy(ESI-MS). A content determination method was established by ultraviolet detection. The lipophilicity, 2,2-diphenyl-1-picrylhydrazy free radical(DPPH) scavenging capacity, anti-coagulant effects, anti-bacterial activity, cytotoxicity, in vitro anti-proliferative activity against tumour cells, and the ability of the compounds to promote the proliferation of chondrocytes were evaluated. The results indicate that CSs exhibit strong DPPH scavenging activity, high lipophilicity, good anti-coagulant activities, wide anti-bacterial activity range, low cytotoxicity, and an excellent ability to promote chondrocyte proliferation.     

Syntheses and structures of two novel fluorescent metal–organic frameworks generated from a tridentate donor–acceptor motif ligand

The tridentate organic ligand 4,4′,4′′‐(4,4,8,8,12,12‐hexamethyl‐8,12‐dihydro‐4H‐benzo[9,1]quinolizino[3,4,5,6,7‐defg]acridine‐2,6,10‐triyl)tribenzoic acid ( H₃L ) has been synthesized (as the methanol 1.25‐solvate, C₄₈H₃₉NO₆·1.25CH₃OH). As a donor–acceptor motif molecule, H₃L possess strong intramolecular charge transfer (ICT) fluorescence. Through hydrogen bonds, H₃L molecules construct a two‐dimensional (2D) network, which pack together into three‐dimensional (3D) networks with an ABC stacking pattern in the crystalline state. Based on H₃L and M(NO₃)₂ salts (M = Cd and Zn) under solvothermal conditions, two metal–organic frameworks (MOFs), namely, catena‐poly[[triaquacadmium(II)]‐μ‐10‐(4‐carboxyphenyl)‐4,4′‐(4,4,8,8,12,12‐hexamethyl‐8,12‐dihydro‐4H‐benzo[9,1]quinolizino[3,4,5,6,7‐defg]acridine‐2,6‐diyl)dibenzoato], [Cd(C₄₈H₃₇NO₆)(H₂O)₃]_n, I , and poly[[μ₃‐4,4′,4′′‐(4,4,8,8,12,12‐hexamethyl‐8,12‐dihydro‐4H‐benzo[9,1]quinolizino[3,4,5,6,7‐defg]acridine‐2,6,10‐triyl)tribenzoato](μ₃‐hydroxido)zinc(II)], [Zn₂(C₄₈H₃₆NO₆)(OH)]_n, II , were synthesized. Single‐crystal analysis revealed that both MOFs adopt a 3D structure. In I , partly deprotonated HL ^2? behaves as a bidentate ligand to link a Cd^II ion to form a one‐dimensional chain. In the solid state of I , the existence of weak interactions, such as O—H…O hydrogen bonds and π–π interactions, plays an essential role in aligning 2D nets and 3D networks with AB packing patterns for I . The deprotonated ligand L ^3? in II is utilized as a tridentate building block to bind Zn^II ions to construct 3D networks, where unusual Zn₄O₁₄ clusters act as connection nodes. As a donor–acceptor molecule, H₃L exhibits fluorescence with a photoluminescence quantum yield (PLQY) of 70% in the solid state. In comparison, the PL of both MOFs is red‐shifted with even higher PLQYs of 79 and 85% for I and II , respectively.